The invention relates to ceramic dielectric materials which can be fired at relatively low temperatures. The invention also relates to multilayer capacitors utilizing such dielectric materials in layers separated by electrodes. The electrodes are made of alloys which remain solid at the firing temperature and which remain substantially metallic (nonoxidized) throughout firing. Moreover, the invention relates to a method of manufacturing such dielectric materials and multilayer capacitors.
In the past, ceramic capacitors have been made in various forms. These forms include disc capacitors and multilayer capacitors. In disc capacitors, preparation and firing of the ceramic dielectric precedes and is separate from the step of applying the electrodes to the dense ceramic dielectric. In contrast, in the production of multilayer capacitors the electrodes are applied to a green ceramic, after which the entire ceramic/electrode combination is fired. Thus, multilayer capacitors impose additional constraints on capacitor production. In multilayer capacitors the electrodes must be able to withstand firing (i) without reacting with the ceramic, (ii) without reacting with the firing atmosphere, and (iii) without melting.
For example, a general purpose ceramic dielectric composition is disclosed in U.S. Pat. No. 3,529,978. This composition is made up essentially of BaTiO.sub.3 with Bi.sub.2 O.sub.3, Nb.sub.2 O.sub.5, TiO.sub.2, and ZnO or MgO. The resulting compositions have dielectric constants generally above 1000 at room temperature, and the temperature coefficient of capacitance is relatively small. The ceramic is fired in a temperature range of 2140.degree.-2340.degree. F. (1170.degree.-1280.degree. C.) depending upon the particular composition used.
While this material alone has good dielectric properties, an attempt to use it in multilayer capacitors may lead to problems. The high firing temperature required to process this material (1170.degree.-1280.degree. C.) necessitates the use of expensive noble metal electrodes which can withstand the high sintering temperatures without melting and without oxidizing. For example, the electrodes may be made of gold, platinum, or palladium. Moreover, in the case of palladium electrodes, the palladium tends to chemically react with the bismuth in the ceramic to produce microcracks and/or voids in the ceramic and to produce discontinuous electrodes. These defects reduce the reliability, insulation resistance, and breakdown voltage of the capacitors. They also increase the dissipation factor of the capacitors, and reduce the lifetime of the capacitors. (Abstract: Precious Metal Electrode Systems for Multilayer Ceramic Capacitors, R. B. Amin et al, National Materials Advisory Board Workshop on Reliability of Multilayer Ceramic Capacitors, March 1982.)
Besides gold, platinum, and palladium, silver electrodes are known to be resistant to oxidation during firing. However, pure silver melts at about 960.degree. C., which is well below the range of firing temperatures used in U.S. Pat. No. 3,529,978.
One possible way of overcoming the problems of the high cost of noble metal electrodes, the bismuth-palladium reaction, and the low melting temperature of silver is by using, for example, silver-palladium alloy electrodes. The bismuth-palladium reaction is reportedly suppressed when the palladium content of such electrodes is less than thirty-five atomic percent (see, Amin et al, supra). Moreover, silver-palladium alloys having less than thirty-five atomic percent palladium are less expensive than either pure palladium or alloys having a higher palladium content. However, because silver-palladium alloys having no more than thirty-five atomic percent palladium melt at temperatures below approximately 1190.degree. C. (see, Constitution of Binary Alloys, M. Hansen, pages 41 and 42, McGraw Hill, 1958), it is necessary to fire multilayer capacitors using such electrodes at temperatures of approximately 1150.degree. C. or less. (This spread between the melting temperature and the firing temperature is provided for two reasons. First, it is provided so that inherent variations in the temperature in the furnace will not allow the "spot" temperature to rise above 1190.degree. C. Second, it is provided to allow for a lowering of the melting temperature of the electrodes due to a diffusion of bismuth into the electrodes from the ceramic.)
Although from the above discussion it appears that good, inexpensive electrodes can be formulated, the ceramic disclosed in U.S. Pat. No. 3,529,978 must be fired at a temperature between 1170.degree.-1280.degree. C. This firing temperature range is too high for use of the proposed silver-palladium electrodes in a multilayer capacitor. At these temperatures, the electrodes will melt and thereby render the resulting product useless as a multilayer capacitor. Moreover there is evidence (e.g. Amin et al, supra) that there may be a destructive bismuth-palladium reaction producing further harm to the electrodes at these firing temperatures.